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81.
Gerhard Laus Johannes Schütz Herwig Schottenberger Max Andre Klaus Wurst Mariana Spetea Karl‐Hans Ongania AdrianG. Müller Helmut Schmidhammer 《Helvetica chimica acta》2003,86(10):3274-3280
The two diastereoisomeric ferrocenyl‐substituted orvinols 2 and 3 were prepared. The modified alkaloids are still able to interact with opioid receptors (see Table). The ferrocene moiety allows highly selective and sensitive electrochemical detection. The X‐ray crystal structure of the major isomer 2 was determined. The combination of a metallocene and a morphinan alkaloid holds promise for useful antitumor activity. 相似文献
82.
The decays of3 S 1 quarkonia into a photon and a scalar or pseudoscalar Higgs particle are examined, taking into account the bound-state dynamics in the framework of a nonrelativistic potential model. We find that for realistic quark potentials the naive calculation [1] overestimates the scalar rate. Numerical results are obtained for the \(\bar bb\) and \(\bar tt\) quark systems. 相似文献
83.
84.
[reaction: see text] The fluorescence quenching of 2,3-diazabicyclo[2.2.2]oct-2-ene (DBO) by nucleotides has been studied. The quenching mechanism was analyzed on the basis of deuterium isotope effects, tendencies for exciplex formation, and the quenching efficiency in the presence of a molecular container (cucurbit[7]uril). Exciplex-induced quenching appears to prevail for adenosine, cytidine, and uridine, while hydrogen abstraction becomes competitive for thymidine and guanosine. Compared to other fluorescent probes, DBO responds very selectively to the type of nucleotide. 相似文献
85.
The reaction of C5H5Rh(CO)(PiPr3) (1] which is prepared from C5H5Rh(CO)2 and neat P1Pr3, with the nitriloxides 2-RC6H4CNO (R = H, Cl) leads to the formation of the metallaheterocycles C5H5(P1Pr3)
) (2, 3) in 90–95% yield. Compound 1 reacts with tosylazide to give the C,N-bound isocyanate complex C5 H5(PiPr3)Rh(η2-TosN=C=O) (6). Analogously, on treatment of C5Me5Co(CO)(PMe3) with phenylazide the phenylisocyanate derivative C5Me5(PMe3)Co(η2-PhN=C=O) (7) is formed. Protonation of 7 with CF3CO 2H affords the non-ionic carbamoylcobalt complex C5Me5(PMe3)Co[C(O)NHPh](O2CCF3) (8). The X-ray structural analysis of 2 reveals the presence of an almost planar
heterocycle in which the two Rh-C distances differ by 0.045 Å 相似文献
86.
Five different structures of CH5
+ and one structure of CH5
– are calculated using a gaussian basis both in the SCF approximation and with the inclusion of electron correlation in the independent electron pair approximation (IEPA). While on SCF level the C
sstructure of CH5
+ has to lowest energy, the energy difference between the C
sand C
2vstructures becomes negligible if correlation is included. In contrast to this the approach of a proton to CH4 at large and intermediate distances is most favorable towards a corner of the CH4 tetrahedron which means a structure. The decomposition of CH5
+ into CH3
+ and H2 requires 20kcal/mol on SCF level and 40 kcal/mol if correlation is included. 相似文献
87.
Zepeck F Gräwert T Kaiser J Schramek N Eisenreich W Bacher A Rohdich F 《The Journal of organic chemistry》2005,70(23):9168-9174
[Structure: see text]. The IspG protein is known to catalyze the transformation of 2-C-methyl-d-erythritol 2,4-cyclodiphosphate into 1-hydroxy-2-methyl-2-(E)-butenyl 4-diphosphate in the nonmevalonate pathway of isoprenoid biosynthesis. We have found that the apparent IspG activity in the cell extracts of recombinant Escherichia coli cells as observed by a radiochemical assay can be enhanced severalfold by coexpression of the isc operon which is involved in the assembly of iron-sulfur clusters. The recombinant protein was isolated by affinity chromatography under anaerobic conditions. With a mixture of flavodoxin, flavodoxin reductase, and NADPH as the reducing agent, stringent assay methods based on photometry or on 13C NMR detection of multiply 13C-labeled substrate/product ratios afforded catalytic activities greater than 60 nmol mg(-1) min(-1) for the protein "as isolated" (i.e., without reconstitution of any kind). Lower apparent activities were found using photoreduced deazaflavin as an artifactual electron donor, whereas dithionite was unable to serve as an artificial electron donor. The apparent Michaelis constant for 2-C-methyl-D-erythritol 2,4-cyclodiphosphate was 700 microM. The enzyme was inactivated by EDTA and could be reactivated by Mn2+. The pH optimum was at 9.0. The protein contained 2.4 iron ions and 4.4 sulfide ions per subunit. The replacement of any of the three conserved cysteine residues afforded mutant proteins which were devoid of catalytic activity and contained less than 6% of Fe2+ and less than 23% of S2- as compared to the wild-type protein. Sequence comparison indicates that putative IspG proteins of plants, the apicomplexan protozoan Plasmodium falciparum, and bacteria from the Bacteroidetes/Chlorobi group contain an insert of about 170-320 amino acid residues as compared with eubacterial enzymes. 相似文献
88.
Recent developments in quantitative surface analysis by Auger (AES) and x-ray photoelectron (XPS) spectroscopies are reviewed and problems relating to a more accurate quantitative interpretation of AES/XPS experimental data are discussed. Special attention is paid to consideration of elementary physical processes involved and influence of multiple scattering effects on signal line intensities. In particular, the major features of core-shell ionization by electron impact, Auger transitions and photoionization are considered qualitatively and rigorous approaches used to calculate the respective transition probabilities are analysed. It is shown that, in amorphous and polycrystalline targets, incoherent scattering of primary and signal Auger and photoelectrons can be described by solving analytically a kinetic equation with appropriate boundary conditions. The analytical results for the angular and energy distribution, the mean escape depth, and the escape probability as a function of depth of origin of signal electrons as well as that for the backscattering factor in AES are in good agreement with the corresponding Mote Carlo simulation data. Methods for inelastic background subtraction, surface composition determination and depth-profile reconstructions by angle-resolved AES/XPS are discussed. Examples of novel techniques based on x-ray induced photoemission are considered. 相似文献
89.
Fabiano Molinos de Andrade Clovis Peppe Werner Uhl 《Journal of organometallic chemistry》2005,690(5):1294-1299
The reaction of bromomethyl-dibromo-indium(III), Br2InCH2Br with dialkylselenides, R1SeR2 (R1 = CH3, R2 = CH2C6H5; R1 = C2H5, R2 = CH2C6H5; R1 = R2 = CH2C6H5) afforded the corresponding dialkylselenonium methylide complexes of indium tribromide, Br3InCH2SeR1R2, which were fully characterized by NMR spectroscopy and single crystal X-ray diffraction studies. 相似文献
90.
[reaction: see text] The complexation of p-sulfonatocalix[4]arene (CX4) with 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[3.2.2]non-2-ene (3), 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4), and 1-phenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (5) was studied in D2O at pD 7.4 by 1H NMR spectroscopy. The formation of deep inclusion complexes was indicated by large upfield 1H NMR shifts of the guest protons (up to 2.6 ppm), which were also used to assign, in combination with 2D ROESY spectra, a preferential inclusion of the isopropyl group of 4 and a dominant inclusion of the azo bicyclic residue for 5. The bicyclic azoalkanes 1-3 showed exceptionally high binding constants on the order of 1000 M(-1), 1-2 orders of magnitude larger than for previously investigated noncharged organic guest molecules. The strong binding was attributed to the spherical shape complementarity between the guest and the conical cavity offered by CX4. Interestingly, although the derivatives 4 and 5 are more hydrophobic, they showed a 2-3 times weaker binding, which was again attributed to the deviation from spherical shape in these bridgehead-substituted derivatives. The preferential inclusion of the hydrophilic but spherical bicyclic residue of 5 rather than the hydrophobic aromatic phenyl group provides a unique observation in aqueous host-guest chemistry and corroborates the pronounced spherical shape affinity of CX4. 相似文献